1-amino-2-dicarboximidoalkoxy-4-hydroxyanthraquinones



United States Patent 3,394,144 l-AMlNO-Z-DICARBOXIMIDOALKOXY- l-HYDROXYANTHRAQUINONES Ralph R. Giles and Max A. Weaver, Kingsport,Tenn., as-

signors to Eastman Kodak Company, Rochester, N.Y.,

a corporation of New Jersey No Drawing. Filed Sept. 27, 1965, Ser. No.490,725 9 Claims. (Cl. 260-326) ABSTRACT OF THE DISCLOSURE1-amino-4-hydroxyanthraquinone compounds containing adicarboximidoalkoxy group at the 2-position are useful as dyes forhydrophobic textile materials.

This invention relates to novel anthraquinone compounds and moreparticularly to anthraquinone compounds, such as anthraquinonedyestuffs, containing a dicarboximido radical.

The novel dyestuffs of the invention have the general formula wherein Rrepresents a 1-amino-4-hydroxyanthraquinone radical, e.g. a radicalhaving the structure:

II o H R represents a straight or branched-chain alkylene radical, e.g.methylene, ethylene, propylene, butylene, 2,2- dimethyl-propyl, isobutyland the like; cycloalkylene e.g. cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and the like; or alkylene-oxyalkylene, e.g. C H OC H C H OC Hand the 1ike;

R represents a dicarboxirnido radical, e.g. a radical havin g thestructure:

where Z represents the canbon atoms necessary to complete the ring, suchas vinylene e.g. CH=CH--; alkylene, e.g. -CH -CH o-phenylene, e.g.

o halophenylene, e.g.

O1, Br

and the like.

The following are representative dicarboxirnido radicals:

succinimido .phthalimido tetrachloro phtha'limido tetrahydro phthalimidohexahydro phthalimido 3,394,144 Patented July 23, 1968 4-carboxypht-halimido 3-nitro phthalimido 3-methyl phthalimido 3-aminophthalimidoglutarimido bicycl0[2.2.1]-5-heptene-2,B-dicarboximido 1,8-naphthalimidocitraconimido cycloalkanedicarboximido e.g. /O 0 CH2 C 0 CH3 The novelanthraquinone dyes of the invention may be prepared by several methods,including:

(1) Reaction of an imido alcohol with 1-amino-2-aryloxy-4-hydroxyanthraquinone,

(2) Reaction of an imido alcohol with 1-amino-4hydroxyanthraquinone-Z-sulfonic acid or salts thereof, and

(3) Reaction of an imide with 1-amino-2 haloa1koxy-4-hydroxyanthraquinone.

The first method is preferred as will be shown in the followingexamples:

EXAMPLES Example 1.Preparation of N-2- hydroxyethylsuccinirnide Anamount of g. of succinic anhydride was added portionwise to 61 g. of2-aminoethanol. The temperature rose to about 124 C. during theaddition. The material was then heated for 1 hr. at C. and distilledunder vacuum to yield 125.9 g. of product, M.P. 5458 C.

Example 2.Preparation 0t N-3- hydroxypropylsuccinimide The procedure ofExample 1 was repeated, substituting an equimolar quantity of3-aminopropanol-1 for Z-aminoethanol. Vacuum distillation of thereaction mixture yielded 111.8 g. of the product.

Example 3.-Preparation of N-3-(2-hydroxyethoxy) propylsuccinimide Theprocedure of Example 1 was repeated, substituting an equimolar quantityof 3-aminopropoxyethanol for 2- aminoethanol. Vacuum distillation of thereaction mixture yielded 129.1 g. of product.

Example 4.-Preparation of N-2- hydroxyethylphthalimide The procedure ofExample 1 was repeated, substituting an equimolar quantity of phthalicanhydride for succinic anhydride. The reaction mixture was diluted with500 ml. methanol. An amount of 133.0 g. of product was obtained, M.P.125126 C. Evaporation of methanol permitted recovery of an additional37.6 g. of product, M.P. 123-124 C.

Example An amount of 5.0 g. of N-2-hydroxyethylsuccinimide, 0.9 g. ofl-amino-4-hydroxy-2-phenoxyanthraquinone, and 0.25 g. of potassiumhydroxide was heated at l35140 C. for a period of 3 hr., with a slowstream of nitrogen above the surface to aid in the removal of phenol.The material was neutralized with acetic acid and diluted with alcoholso that it could be drowned in water and filtered. The precipitate wasdissolved in acetone and filtered, and the acetone solution was drownedin hexane to precipitate the product. Further purification can beaccomplished by recrystallizing from hot Z-methoxyethanol and dilutingthe solution to obtain the dye. The product is 1-amino-4- hydroxy-2-(2succinimide)ethoxyanthraquinone, which dyes polyesters in a bright,lightfast shade of red, with good resistance to sublimation. It alsodyes cellulose acetate in a bright, light-fast shade, only slightly lessbluish than the polyester.

The above compound may also be prepared by using solvents in addition toa large excess of hydroxyethylsuccinimide such as dimethyl sulfoxide orN-methyl pyrrolidone or a mixture of pyridine and dimethyl formamide.The product had the structure:

The 3-hydroxypropylsuccinimide in Example 6 was replaced byN-hydroxyethoxypropylsuccinimide. The product is1-amino-4-hyrlroxy-2-[2-(3-succinimidopropoxy)- ethoxy]anthraquinone,which dyes polyesters and cellulose acetate in bright, light-fast shadeslike those obtained from the compound of Examples 5 and 6. The producthad the structure:

0 NHz COCHQ C 0 CH2 4 Example 8 An amount of 1.10 g. of potassiumcarbonate and 1.54 g. succinimide was added to 25 ml. dimethyl formamideand heated to C. 0.75 g. of l-amino-2-[2-(2-chloroethoxy)ethoxy] 4hydroxyanthraquinone was added. After 4.5 hr. at 7580 C., the solutionwas poured into 60 ml. of Water, with 10 ml. methanol being used torinse the reactor flask. 10 ml. 5% HCl were used to destroy thealkalinity. The precipitate was filtered out and recrystallized from hotZ-methoxyethauol solution. The product was l-amino 4hydroxy-2-[2-(2-succinimidoethoxy) ethoxy]anthraquinone. The red shadeon polyesters and cellulose acetate exhibited excellent light-fastness,and the dyeings on polyesters showed no sublimation to heat at 350 F.for one minute.

The same compound was obtained by reacting N-2-(2- hydroxyethoxy)ethylsuccinimide with 1-amino-4-hydroxy- Z-phenoxyanthraquinone. Theproduct had the structure:

0 NHz ii I C O C H2 OG2H4O C H4N C O C H;

Example 9 When the succinimide in Example 8 was replaced by phthalimide,and the anthraquinone intermediate in EX- ample 8 was replaced byl-amino-Z-(2-chloro)ethoxy-4- hydroxyanthraquinone, the product was1-amino-4- hydroxy-2-(2-phthalimido)ethoxyanthraquinone. The samecompound was obtained by reacting 1-amino-4-hydroxy'2-phenoxy-anthraquinone with N-Z-hydroxyethyl phtha limide. The producthad the structure:

0 NH, 00 l OC2H4-N Example 10 l-amino 4hydroxy-2-(2-succinimido)ethoxyanthraquinone was prepared from thecorresponding anthraquinone sulfonic acid by the following method: 4.0g. of potassium hydroxide, 15 ml. of N-methylpyrrolidine, 2.0 g. of1-amino-4-hydroxyanthraquinone-2-sulfonic acid, sodium salt and 5.0 g.of N-2-hydroxyethylsuccinimide were reacted at l20-125 C. for 8 hr. Alower yield of product was obtained by this method than by the methodphenoxyanthraquinone, 0.50 g. of potassium hydroxide, and 0.2 ml. ofpyridine was reacted at 162-170 C. for 6 hr. The material was dilutedcarefully with methanol while being cooled. The precipitate was filteredout and recrystallized from 2-methoxyethanol. The product was 1 amino 4hydroxy-2-[(Z-phthalimidoethoxy)ethoxy] anthraquinone. It showed dyeingcharacteristics almost identical with that of the correspondingsuccinimide compound. The product had the structure:

NH: 00 l In accordance with the methods of preparation set forth inExamples through 11, additional anthraquinone dyestuffs were preparedcorresponding to the general formula CO R0R N Z wherein R and Z are setforth in the following table:

TABLE Example R Z 12 CHzCHzCH3CHr- CH2 3Hg 13.- CH2CH2 CH in GH 14--CH2CHa- HC CH2 H% 5112 15 -G1IzCHz- 16 -CH2CH2- C1 17 --HCCHr -CH2 3H32 18... CH2CH2OCH2CH2' --CH 19 --CH CH;O CHgCHz- CHCH3 CHg CHzC1Iz CH220. -CHzC HC 0112- I -CH3 CH5CH2 i -0H= 21 CH3-C-CH2- (|3H2 22 CHzCHzCHn(J-CH3 (ilH2 The anthraquinone compounds of the invention may be usedfor imparting bright red dyeings of excellent fastness to hydrophobicfibers such as linear polyester, cellulose ester, acrylic, modacrylic,polyamide, etc., fibers in the manner described in US. Patents2,880,050, 2,757,064, 2,782,187 and 2,043,827. The following exampleillustrates a method by which the anthraquinone compounds of theinvention can be used to dye polyester textile materials.

0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. ofethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurateand 0.5% sodium lignin sulfonate aqueous solution is added, withstirring, until a fine emulsion is obtained. Water is then slowly addedto a total volume of 200 cc. 3 cc. of Dacronyx (a chlorinated benzeneemulsion) are added and 10 grams of a textile fabric made of Kodelpolyester fibers are entered. The fabric is worked 10 minutes Withoutheat and then for 10 minutes at C. The dye bath is then brought to theboil and held at the boil for one hour. Following this, the fabric isrinsed in warm water, then scoured in aqueous 0.20% soap, 0.2% soda ashsolution. After scouring, the fabric is rinsed With Water and dried.Accordingly, since the anthraquinone compounds of the invention arewater-insoluble, they can be applied from aqueous dispersions in themanner of the so-called dispersed dyes. However, coloration can also beeffected, for example, by incorporating the anthraquinone compounds intothe spinning dope and spinning the fiber as usual. The anthraquinonecompounds of our invention have varying utility as dyes. The degree ofutility varies, for example, depending upon the material being dyed andthe formula of the anthraquinone compound. Thus, for example, all thedyes will not have the same degree of utility for the same material.

Polymeric linear polyester materials of the terephthalate type areillustrative of the linear aromatic polyester textile materials that canbe dyed with the new anthraquinone compounds of our invention. Theterephthalate fibers sold under the trademarks Kodel, Dacron, andTerylene, for example, in the form of filaments, yarn and fabric, forexample, are illustrative of the polyester textile materials that can bedyed. Kodel polyester fibers are more particularly described in US.Patent 2,901,446. Dacron and Terylene polyester fibers are described,for example, US. Patent 2,465,319. The polymeric linear polyestermaterials disclosed in Us. Patents 2,945,010, 2,957,745 and 2,989,363for example, can be dyed. The linear aromatic polyester materialsspecifically named have a melting point of at least 200 C.

Nylon, in fiber, yarn and fabric form, is representative of polyamideswhich can be dyed with the compounds.

The invention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove, and asdefined in the appended claims.

What we claim is:

1. A compound having the formula 0 NH, II I ll 0 OH wherein R=straightor branchedchain alkylene of 1 to 5 carbon atoms,1,4-cyclohexylenedimethylene,

C H OC H or -C2H4OC3H6; v R =a dicarboximido radical. 2. A compoundaccording to claim 1. wherein R =ethylene, propylene, --C H OC H or C HOC H and R =a dicarboximid-o radical having the formula f3 --N /Zwherein Z=vinylene, ethylene, propylene, o-phenylene, or o-halophenylene.

3. The compound having the formula:

NIT:

C-Cllz 4. The compound having the formula:

hF-Cll; O

5. The compound having the formula:

6. The compound having the formula:

06 1140 CzHaN 8 7. The com-pound having the formula:

0 O Nllz II I o-o1r i i ("l-CH2 I 0 10 (I) OH 8. The compound having theformula:

0 NH; II I /COCH2 OCH4O 0mm i l 00 H: Y I

9. The compound having the formula:

0 NH; 00 A l o1 OCzH N 01 ll 6H References Cited UNITED STATES PATENTS1,915,334 6/1933 Salsberg et al. 260-243 2,075,359 3/1937 Salsberg et al16722 30 3,184,455 5/1965 Nee). 260243 NICHOLAS S. RIZZO, PrimaryExaminer.

JOSE TOVAR, Assistant Examiner,

